Production of cycloolefinic hydrocarbons and aromatic hydrocarbons



' ing cyclic hydrocarbons.

Patented Dec. 26, 1944 raonoc'non or CYCLOOLEFINIC HYDRO- CARBONS AND BONS AROMATIC HYDROCAB- Herman Pines and Vladimir N. Ipatiefl', Riverside,-Ill., assignors to Universal Oil. Products Company, Chicago, Ill.,a. corporation of Dela.-

ware

No Drawing. Application June 12, 1944,

Serial No. 540,008

8 Claims.

This invention relates to a process for produc- More specifically, the invention relates to a process for producing cycloolefins by condensing a glycol of at least 4 carbon atoms with an olefin.

An object of this invention is the condensation of an oleflnic hydrocarbon with a glycol containing at least 4 carbon atoms per molecule.

Another object of this invention is the production of a cyclohexene hydrocarbon by condensing a mono-olefinic'hydrocarbon with a gly-. col containing at least 4 carbon atoms per mole cule. I

A further object of this invention is the production of 1,3,5-trimethylcyclohexene by condensing 2-methylpentanediol-2,4 with propylene.

One specific embodiment of this invention relates to a process for producing a cyclo-olefin which comprises condensing an aliphatic monoolefin with a glycol having at least 4 carbon atoms per molecule at a temperature of from about 150 to about 400 C.

A further embodiment of this invention relates to a process which comprises condensing a mono-olefin with a cyclic glycol having at least 4 carbon atoms per molecule.

Cyclohexene and different alkyl cyclohexene hydrocarbons which are obtainable by the process of our invention may be hydrogenated to cyclohexane hydrocarbons, or be dehydrogenated to benzene and alkylated benzene hydrocarbons.

By the term condensation used in this specification and in the claims, we mean the chemical combination of a glycol of at least 4 carbon atoms with an olefin accompanied by the splitting out character of results obtained by the process of iii our invention, although the data presented are not introduced with the intention of unduly restricting the broad scope of the invention.

Ethylene, under an initial pressure of 40 atmospheres at 25 C. was introduced to a'steel autoclave of 450 cc. capacity containing 58.4 grams of 2-methylpentanediol-2,4 and heated at 200 C. The product formed in this reaction was found to consist of 40 grams of normally liquid hydrocarbons and 35 cc. (approximately 22 grams) of liquefied condensible gases. About 25 of the normally liquid hydrocarbon product boiled between 124 and 135 C. and comprised essentially dimethylcyclohexene, which by hydrogenation and subsequent dehydrogenation over platinized alumina catalyst yielded meta-xylene. About of the liquefied condensible gas was isobutylene.

The novelty and utility of the process of the present invention are evident from the preceding specification and example, although neither section is intended to limit unduly the broad scope of our invention.

We claim as our invention:

1. A process for producing a cyclo-olefinic hydrocarbon which comprises reacting a glycol having at least 4 carbon atoms per molecule and an olefinic hydrocarbon at a sufficient temperature Olefinic alcohols or partially dehydrated glycols such as 2-methylpentene-1-ol-4, are also useful' raw materials for our condensation process.

The olefins usable in our process are prefer- 4 carbon atoms per molecule at a temperature oi from about 150 to about 400 C. and at a superatmospheric pressure of from about 10 to about 100 atmospheres.

4. A process for producing a cyclo olefinic hy" drocarbon which comprises reacting more than one molecular proportion of a mono-oleflnic hydrocarbon and one molecular proportion of a glycol having at least 4 carbon atoms per mole- 7. A process for producing a benzene hydrocarbon which comprises condensing a mono-oleflnic hydrocarbon and a glycol containing at least 4 carbon atoms per molecule to produce a cyclohexene hydrocarbon, hydrogenating said cyclohexene hydrocarbon to a cyclohexane hydrocarbon, dehydrogenating the latter hydrocarbon to a benzene hydrocarbon and hydrogen, and utilizing at least a portion of said hydrogen in the hydrogenation of the cyclohexene hydrocarbon.

8. A process'for producing a benzene hydrocarbon which comprises condensing a mono-oleflnic hydrocarbon and a glycol containing at least 4 carbon atoms per molecule to produce a cyclohexene hydrocarbon and dehydrogenating said cyclohexene hydrocarbon to a benezene hydrocarbon.

HERMAN PINES.

VLADIMIR N. IPATIEFF. 

